Difluoroamino substituted cyclohexane

ABSTRACT

1. A process for the preparation of the bis(difluoramino) compounds which comprises reacting consisting of a ketone selected from the group consisting of acetone, cyclohexanone and cyclohexan-1,4-dione with difluoramine alone to give the hydroxy (difluoramino) derivative of the ketone, and then of reacting said derivative with difluoramine in the presence of an acid selected from the group consisting of fluorosulphonic acid and chlorosulphonic acid to give the bis(difluoramino) compounds.

United States Patent 72 I Inventors Andrew Harper Dlnwoodie Dalry;

James Grigor, Coatbridge, both of Scotland [2!] Appl. No. 240,772 [22] Filed Nov. 27, 1962 Nov. 30, 1971 The United States oi America as represented by the Secretary of the Navy [45] Patented [73] Assignee [32] Priority Nov. 30, 1961 [3 3] Great Britain [3!] 42,971/61 [51] Int.Cl C07c 85/08 Primary Examiner Leland A. Sebastian Attorneys-R. S. Sciascia and A. L. Branning CLAIM: l. A process for the preparation of the bis(difluoramino) compounds which comprises reacting consisting of a ketone selected from the group consisting of acetone, cyclohexanone and cyclohexan-l,4-dione with difluoramine alone to give the hydroxy (difluoramine) derivative of the ketone, and then of reacting said derivative with difluoramine in the presence of an acid selected from the group consisting of fluorosulphonic acid and chlorosulphonic acid to give the bis(difluoramino) compounds.

DIFLUOROAMINO SUBSTITUTED CYCLOHEXANE The present invention relates to the preparation of bis(difluoramino) derivatives of ketones.

Such derivatives find utility as propellent explosive ingredients. It has been proposed to prepare such compounds by refluxing a ketone with difluoramine in the presence of sulfuric acid. Our copending U.S. Pat. application No. 235,885 new Pat. No. 3,432,554 describes processes in which boron trifluoride is substituted for the sulfuric acid in order to facilitate the purification of the reaction products.

According to the present invention, the bis(difluoramino) derivative of acetone, cyclohexanone or cyclohexane-1,4- dione is prepared by refluxing the ketone with difluoramine in the presence of fluorosulfonic acid or chlorosulfonic acid.

The reaction may be carried out with the mere reaction media or may alternatively be carried out in solution or dispersion in inert liquids.

lt may be preferred to carry out the reaction in two stages by first reacting the ketone with difluoramine alone to give the hydroxy(difluoramino) derivative of the ketone which is then reacted with difluoramine together with the fluorosulfonic or chlorosulfonic acid.

The nature of the present invention will be more fully understood if reference is made to the following examples:

EXAMPLE 1 crystallized out, and was found to have the following properties:

Analysis-found C. 24.8%. H. 2.8%. N. [9.8%,

calculated for C H NJ C, 25.0%, H. 2.8%. N. l9.5%, F. 52.8%

Melting point lO7-l08 C. Density 1.7 g./cc.

lmpact Sensitivity l Kg. Mild Steel hammer/Mild steel 10-20 cm.

Thermally stable to 220 C. but burns very rapidly with a fierce flame when ignited.

Soluble in diethyl ether, ethyl alcohol, dichloromethane, nitroglycerine.

EXAMPLE 2 Seventy m. moles acetone was dissolved in 10 cc. dichloromethane and was stirred whilst approximately g. liquid difluoramine, again produced by condensation of gaseous difluoramine on a cold finger condenser at -80 C., was refluxed on to the solution. When the reflux action had been established for about minutes, 71 m. moles of fluorosulfonic acid was slowly added dropwise, and the reflux then continued for a further 4 hours. Excess difluoramine was again removed at the end of the reaction time by purging with nitrogen. The reaction mixture was poured on to 10 g. ice and shaken vigorously in a separating funnel. A lower layer amounting to l5 cc. was removed and dried over anhydrous sodium sulfate. Evaporation of the dichloromethane reduced the volume to 4.5 cc. which was found to be 30 m. moles 2,2-

bis(difluoramin0) propane, CH 'C(NF,),CH This was found to have the following properties:

Analysis-found c, 24.0%. H, 4.5%. N. 19.3%. F. 51.5%

calculated for C,H.N|F4

c. 24.6%. H.4.l%. N. 19.2%. F. 52.0%

A liquid boiling at 71 C. at 760-mm. pressure and soluble in diethyl ether. ethyl alcohol, dichloromethane.

Thermally stable to 220 C., but burns rapidly and fiercely on ignition.

EXAMPLE 3 Sixteen moles of cyclohexanone was dissolved in 5 cc. dichloromethane and treated with approximately 5 g. difluoramine and 17 m. moles of fluorosulfonic acid in the manner described in example 2. Following removal of the dichloromethane 7 m. moles were produced.

This showed the following properties:

Analysis-found C, 38.5%. H, 5.9%. N. 15.2%. [140.7%

calculated for C H Nf C. 38.7%. H. 5.4%. N. 151%. F. 40.9%

A liquid boiling at 165 C. at 760 mm. pressure and soluble in diethyl ether, ethyl alcohol, dichloromethane.

Thermally stable to 220 C. but ignites to burn rapidly with a fierce flame.

EXAMPLE 4 Two m. moles l,4-dihydroxy-l,4-bis(difluoramino) cyclohexane was dissolved in 3 cc. fluorosulfonic acid and treated with difluoramine as in example 1. The product was 1.1 m. moles l, l ,4,4-tetrakis( difluoramino) cyclohexane, having the properties outlined in example 1.

EXAMPLE 5 Four m. moles cyclohexane-l,4-dione was dissolved in 10 cc. dichloromethane and approximately 5 g. liquid difluoramine, produced by condensation of gaseous difluoramine on a cold finger condenser at C.. was allowed to reflux on to the solution. When the reflux action had been established for about ten minutes, l cc. chlorosulfonic acid was slowly added dropwise, and the reflux continued for a further 4 hours. Excess difluoramine was then removed by purging with a slow stream of nitrogen. The black oily reaction mixture was poured into 10 cc. ice water, extracted with dichloromethane, and the extract dried and evaporated to give a pale brown solid. This solid was shown by its infrared spectrum, sublimation and analysis to contain 0.7 m. moles, l,l,4,4-tetrakis(difluoramino) cyclohexane, again having the general properties described in example 1.

EXAMPLE 6 Twenty-five m. moles cyclohexanone was dissolved in 10 cc. dichloromethane and treated with approximately 5 g. difluoramine and 2 cc. chlorosulfonic acid in the manner described in example lb. Following removal of the dichloromethane, 15 m. moles l,l-bis(difluoramino) cyclohexane were isolated, and this had the general properties described in example 3.

What we claim is:

l. A process for the preparation of the bis(difluoramino) selected from the group consisting of fluorosulfonic acid and compounds which comprises reacting a ketone selected from chlorosulfonic acid to give the bis( difluoramino) compounds. the group Consisting of acetone cyclohexanone and cyclohex' 2. A process according to claim 1, wherein the reaction is an-l,4-dione with difluoramine alone to give the hydroxy (difluoramino) derivative of the ketone. and then of reacting 5 said derivative with difluoramine in the presence of an acid carried out in an inert liquid. 

1. A PROCESS FOR THE PREPARATION OF THE BIS(DIFLUORAMINO) COMPOUNDS WHICH COMPRISES REACTING CONSISTING OF A KETONE SELECTED FROM THE GROUP CONSISTING OF ACETONE, CYCLOHEXANONE AND CYCLOHEXAN-1,4-DIONE WITH DIFLUORAMINE ALONE TO GIVE THE HYDROXY (DIFLUORAMINO) DERIVATIVE OF THE KETONE, AND THEN OF REACTING SAID DERIVATIVE WITH DIFLUORAMINE IN THE PRESENCE OF AN ACID SELECTED FROM THE GROUP CONSISTING OF FLUOROSULPHONIC ACID AND CHLOROSULPHONIC ACID TO GIVE THE BIS(DIFLUORAMINO) COMPOUNDS.
 2. A process according to claim 1, wherein the reaction is carried out in an inert liquid. 